Cellulose ether recovery



, Patented June 2 1, 1938 2 121 732 UNITED STATES PATENT QFFlC E CELLULOSE ETHER RECOVERY William'R. Collings, Midland, Mich., assignor to The Dow Chemical Company, Midland, Mich, a corporation of Michigan No Drawing. Application August 1, 1936, Serial No. 93,763

2 Claims. (01. 260-152) This invention relates to a method for the In carrying out this reaction it is customary to treatment of the product obtained by the etheriuse a considerable excess of ethyl chloride; and fication of alkali cellulose with an alkyllhalide, as a result the reaction product contains unand more particularly to a method for the recovreacted ethyl chloride as well as considerable 5 cry of ethyl cellulose from the product obtained ethyl alcohol and ethyl ether. The ethylation 5 during the reaction of alkali cellulose with ethyl reaction is normally carried out by heating under chloride. v pressure at temperatures of about 110l40 C.

The etherification of alkali cellulose with alkyl According to my procedure the reaction product v halides such as methyl bromide, ethyl chloride, is preferably discharged from the ethylator unpropyl chloride, etc., produces a reaction pro-duct der pressure into a vapor-liquid mixture of an 10 containing cellulose ether, some unreacted etherialcohol, such as methyl, ethyL-or propyl alcohol, tying agent, the'alcohol and ether corresponding having sufficient available heat content to vaporto the etherifying agent, and alkali halide. It is ize the unreacted etherifying agent from the among the objects of the invention to provide a reaction mixture. The mixing of the ethyl cellumethod for treating said reaction product wherelose reaction product with the hot alcohol is 15 by the alkyl ether of the cellulose is obtained preferably'carried out ina relatively small chamdirectly therefrom in a solution wherein it can be 'ber wherein the ethylator discharge and the alcopurified or otherwise treated. Another object of hol are violently agitated during the mixing procthe invention is to provide amethod whereby ess, suffi cient alcohol being used to provide the the unreactedetherifying agent can be recovered additional heat required to vaporize the ethyl substantially quantitatively from said reaction chloride from the mixture, and to retain ethyl product. Still a further object of the invention cellulose in solution. The resultant hot mixture 'is to provide a method of separating the alkali is then led into a'second chamber, under lower halide from the above-described reaction product. pressure, the more volatile constituents, e. g.,

I have now found that the cellulose ether can ethyl chloride, ethyl ether, being flash-evaporated 25 be separated from such reaction product accordfrom'the mixture, as well as a quantity of alcohol ing to the hereinafter-described"procedure withand water, and the vapors collected in any conout unfavorably changing the physical characvenient mannen'leaving the alcoholic cellulose .teristics of the ether. The reaction product ether solution containing alkali halide suspended from the etherification step is mixed with a quantherein. This solutionis then filtered to remove 30 tity of a monohydric lower aliphatic alcohol, such the salt and any fibers of unreacted cellulose alcohol being heated substantially toits boiling which may be present therein, after which it can point under the pressure employed. Ordinarily be further treatedin known manner to recover super-atmospheric pressure is used, although the the ethyl cellulose. The hot alcohol may, howoperation may be carried out at normal or sub ever, be supplied directly to the ethylator, and 35 atmospheric pressure. The alkali halide is prethe alkali halide suspension led therefrom to a cipitated from the reaction mixture and the flash chamber, if the ethylator is large enough other products of the reaction are dissolved in to permit the introduction of sufficient alcohol the alcohol. The suspension of the alkali halide thereinto to accomplish the desired result.

in such solution is then led into an expansion The following example is illustrative of th 40 chamber where the pressure is reduced and the practice of the invention; 'unreacted etherifying agent flash-evaporates A reactor was charged W 356 P01111015 0f therefrom. Some water, alcohol and ether of the alkali QH SG Containing Pe cent of celluying age t, Which are present in the relose, 55.3 per c'entof sodium hydroxide, 16.9 per action mixture, and some of the hot alcohol cent of water; a f -qr r cent f sodium ch10 45 employed, may also flash-evaporate, or may be riden thoroughlymiXed W 1250 Pounds of carried out in the vapors leaving said expansion ethyl c o ee e y at on 0f the cellulose chamber. This leaves in the chamber a suspenwas accomplished by heating the mixture at a 'sion of the alkali halide in an alcoholic solution temperature of 115 C. under a pressure of 225 of the cellulose ether which may then readily be pounds gauge for about 7 hours. At the end of 50 filtered to separate the solid alkali halide. this time the reactor contents, cooled to a tem- My process is applicable to the separation of perature of about C., were fed at a uniform ethyl cellulose from the mixed products obtained rate over a period of 30 minutes into a stream by the reaction of alkali cellulose with an excess of per cent ethyl alcohol supplied at its boiling 55 of an ethylating agent, such as ethyl chloride. temperature under 30 pounds gauge pressure. 55

The hot mixture was immediately introduced into,

an expansion chamber to reduce the pressure thereon, so that ethyl chloride and ethyl ether were flashed off, the vapor leaving the expansion chamber under a pressure of 20 pounds gauge. The quantity of ethyl alcohol used was approximately 1790 pounds. The vapors from the expansion chamber were run through a condenser to recover the ethyl chloride and ethyl ether. The composition of the alcoholic ethyl cellulose solution was: alcohol 82 per cent, ethyl cellulose 5.0 per cent, suspended salt 7.5 per cent, dissolved salt 0.5 per cent, the remainder containing traces of water, etheriiying agent, and ether of the etherifying agent. The cellulose ether was recovered from this mixture by precipitation in water after the suspended salt had been filtered jout.

While the above example describes the use of ethyl alcohol in the separation of the ethyl cellulose from the mixed products of etherification, other monohydric alcohols such as methyl, propyl, etc., or mixtures of the same, have also been found suitable for my purpose. The process may also be applied to the separation of other cellulosic ethers such as methyl cellulose, propyl cellulose, ethyl propyl cellulose, etc., from the products of etherification reactions yielding the same. In a modification of the above-described procedure, a hot alcoholic solution comprising the reaction products can first be filtered to remove the salt and thereafter manipulated to flash off residual etherification agent, ether, etc. Furthermore, it is not essential that the ethylator product be mixed with the hot alcohol under super-atmospheric pressures, since, if desired, the mixing step may be carried out at atmospheric or sub-atmospheric pressures, and the resulting cellulose ether solution thereafter introduced into an evacuated expansion chamber, thereby flashevaporating olf the more volatile constituents. If desired, various purification and/or bleaching steps, etc., may be carried out on the suspension prior to the removal of salt therefrom, and any solid, alcohol-insoluble material added for such purpose removed along with the salt on filtration.

My method of separating cellulose ethers from the crude etherification product possesses, among others, the following advantages: (1) the cellulose ether is recovered from the crude reaction product in alcoholic solution and may be purified as such, thereby eliminating the steps of separation, washing, drying, and subsequent dissolving of the cellulose compound in alcohol usually required before purification; (2) the unreacted etherifying agent can be substantially quantitatively recovered in an efficient and economical manner; (3) the method lends itself readily to adaptation as a continuous process; (4) the suspended salt serves as a filter aid in removing unreacted cellulose and undesirable gelatinous masses from the product during the filtration step; and (5) under the mild conditions of. treatment prevailing during the separation, the char acteristics of the cellulose ether are not materially altered, e. g. degradation is minimized.

This application is a continuation in part of my co-pending application Serial No. 93,428, filed July 30, 1936.

Other modes of applying the principle of my invention may be employed instead of the one explained, change being made as regards the method herein disclosed, provided the step or steps stated by any of the following claims or the equivalent of such stated step or steps be employed.

I therefore particularly point out and distinctly claim as my invention:

1. In a method of treating the product obtained by reacting alkali cellulose with an excess of an alkyl halide at an elevated temperature and under super-atmospheric pressure, the steps which consist in mixing said reaction product with a sulficient quantity of, a lower monohydric aliphatic alcohol to retain said ether in solution when the residual etherifying agents and volatile byproducts are removed therefrom, said alcohol being a liquid having a boiling point above that of said etherifying agent, and being supplied at a temperature and pressure such that the mixture obtained has a heat content sufficient to vaporize said residual etherifying agent when the pressure on the mixture is reduced; reducing the pressure on the so-formed mixture to flash 01f unchanged etherifying agent and other constituents of the reaction mixture which are more volatile than the alcohol employed, whereby the cellulose ether is subjected to a solvent exchange wherein the lower boiling solvent, comprising the residual etherifying agent, is removed and the cellulose ether remains in solution in the relatively higher coiling alcoholic solvent, while the alkali metal halide, formed in the reaction, is undissolved.

2. In a method of treating the product obtained by reacting alkali cellulose with an excess ofv ethyl chloride at an elevated temperature and under super-atmospheric pressure, the steps which consist in mixing said reaction product comprising ethyl cellulose with a sufiicient quantity of a lower monohydric aliphatic alcohol to retain said ethyl cellulose in solution when the residual ethyl chloride and volatile by-products are removed therefrom, said alcohol being a liquid having a boiling point above that of said ethyl chloride, and being supplied at a temperature and pressure such that the mixture obtained has a heat content sufficient to vaporize said residual ethyl chloride when the pressure on the mixture is reduced; reducing the pressure on the soformed mixture to flash off unchanged ethyl chloride and other constituents of the reaction mixture which are more volatile than the alcohol employed, whereby the ethyl cellulose is subjected to a solvent exchange wherein the lower boiling solvent comprising the residual ethyl chloride is removed and the ethyl cellulose remains in solution in the relatively higher boiling alcoholic solvent, while the sodium chloride formed in the reaction is undissolved.

WILLIAM R. COLLINGS. 

